4-(substituted)amino-3-arylpyrrolinone derivatives

ABSTRACT

The invention relates to new 4-(substituted)amino-3-arylpyrrolinone derivatives of the general formula (I) ##STR1## in which X, Y, Z, n, B, M, L and A are as defined in the description, to a process and new intermediates for their preparation, and to their use as herbicides.

The invention relates to new 4-(substituted)amino-3-arylpyrrolinonederivatives, to processes and new intermediates for their preparation,and to their use as herbicides.

3-Acyl-pyrrolidine-2,4-diones have previously been described as havingpharmaceutical properties (S. Suzuki et. al., Chem. Pharm. Bull. 15 1120(1967)). N-Phenyl-pyrrolidine-2,4-diones were furthermore synthesised byR. Schmierer and H. Mildenberger, Liebigs Ann. Chem. 1985 1095. Abiological activity of these compounds was not described.

EP-A 0,262,399 discloses compounds which have a similar structure(3-aryl-pyrrolidine-2,4-diones), but they are not known as having aherbicidal activity.

EP-A-0,415,185 discloses 4-alkoxy or 4-substitutedamino-3-arylpyrrolinone derivatives and their use as herbicides.

EP-A 377,893 furthermore describes 3-arylpyrrolidine-2,4-dionederivatives which have an insecticidal, acaricidal and herbicidal actionand which may have a hydroxyl in the 4-position of the pyrrolinone.Compounds listed in the abovementioned application EP-A-415,185 by nameare excluded from the extent of protection of the present application bydisclaimer.

There were now found new 4-(substituted)amino-3-arylpyrrolinonederivatives of the general formula (I) ##STR2## in which X and Yindependently of one another represent hydrogen, halogen, alkyl, alkoxy,alkylthio, halogenoalkoxy, halogenoalkyl, or in each case represent anunsubstituted or substituted radical from the series comprising aryl,aryloxy or arylthio,

Z represents halogen, alkyl or alkoxy,

n represents a number 0, 1, 2 or 3,

A represents a radical from the series comprising alkyl, alkenyl,alkinyl, alkoxyalkyl, halogenoalkyl, polyalkoxyalkyl or alkylthioalkyl,each of which is unsubstituted or each of which is substituted byhalogen, or represents cycloalkyl which is optionally interrupted byhetero atoms, or represents arylalkyl which is unsubstituted orsubstituted by halogen, alkyl, halogenoalkyl, alkoxy and/or nitro, oraryl which is unsubstituted or substituted by suitable substituentsbeing halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, or phenoxyor phenylthio, each of which is unsubstituted or substituted by halogen,alkyl, alkoxy, halogenoalkyl and/or halogenoalkoxy,

B represents hydrogen, the group ##STR3## or the group ##STR4## Lrepresents hydrogen, or represents an optionally halogen-substitutedradical from the series comprising alkyl, alkenyl, alkinyl,polyalkoxyalkyl, alkoxyalkyl, alkylthioalkyl, cycloalkyl which isoptionally interrupted by hetero atoms, or represents a radical from theseries comprising aryl, arylalkyl or hetaryl, each of which isoptionally substituted by halogen, alkyl, halogenoalkyl, alkoxy ornitro,

M represents hydrogen, alkyl or alkoxyalkyl, or

A and L or L and M together with the atoms to which they are bonded forma cycle and

R represents an optionally halogen-substituted radical from the seriescomprising alkyl, alkenyl, alkinyl, alkoxyalkyl, polyalkoxyalkyl,alkylthioalkyl, cycloalkyl which is optionally interrupted by heteroatoms, or represents an aryl which is optionally substituted by halogen,alkyl, halogenoalkyl, alkoxy or nitro,

and the enantiomeric forms of compounds of the formula (I) with theexception of the compounds4-amino-1-isopropyl-3-(3-trifluoromethylphenyl)-3-pyrrolin-2-one and4-amino-1-cyclopropyl-3-(3 -trifluoromethylphenyl)-3-pyrrolin-2-one (EP0,415,185).

Other sub-groups which may be defined are the following: (Ia): compoundsof the formula (I) in which B=hydrogen (Ib): compounds of the formula(I) in which B=--COR (Ic): compounds of the formula (I) in whichB=--COOR.

The aliphatic hydrocarbon chains such as, for example, alkyl,halogenoalkyl, arylalkyl or phenoxyalkyl, are in each casestraight-chain or branched.

In the case of substituted systems such as, for example, substitutedalkyl, alkenyl, cycloalkyl or aryl, these may in each case bemonosubstituted or polysubstituted by identical or differentsubstituents. Aromatic systems are preferably monosubstituted topentasubstituted, in particular monosubstituted to trisubstituted, andcyclic systems are preferably monosubstituted to octasubstituted, inparticular monsubstituted to pentasubstituted.

Furthermore, it has been found that the compounds of the formula (Ia)##STR5## in which aα) B represents hydrogen and in which the radicals A,L, M, X, Y and Z_(n) have the abovementioned meanings, are obtained when4-hydroxypyrrolinones of the formula (II) ##STR6## in which A, L, M, X,Y, Z and n have the abovementioned meanings, are reacted with ammonia orammonia salts, if appropriate in the presence of a diluent, ifappropriate in the presence of a catalyst and if appropriate in thepresence of a dehydrating agent, or in that

aβ) compounds of the formula (III) ##STR7## in which A, L, M, X, Y, Zand n have the abovementioned meanings, are subjected to intramolecularcyclisation in the presence of a diluent and in the presence of a base.

Furthermore, it has been found that compounds of the formula (Ib)##STR8## in which A, L, M, R, X, Y, Z and n have the abovementionedmeanings, are obtained when compounds of the formula (Ia) ##STR9## inwhich A, L, M, X, Y, Z and n have the abovementioned meanings, bα) arereacted with acid halides of the general formula (IV) ##STR10## in whichR has the abovementioned meaning and

Hal represents halogen, in particular chlorine and bromine, ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent, or

bβ) are reacted with carboxylic anhydrides of the general formula (V)

    R--CO--O--CO--R                                            (V)

in which

R has the abovementioned meaning, if appropriate in the presence of adiluent and if appropriate in the presence of an acid-binding agent.

(c) Furthermore, it has been found that compounds of the formula (Ic)##STR11## in which A, L, M, X, Y, Z, R and n have the abovementionedmeanings, are obtained when compounds of the formula (Ia) ##STR12## inwhich A, L, M, X, Y, Z and n have the abovementioned meanings, arereacted with chloroformate of the general formula (VI)

    R--O--CO--Cl                                               (VI)

in which

R has the abovementioned meaning, if appropriate in the presence of adiluent and if appropriate in the presence of an acid-binding agent.

Finally, it has been found that the new4-(substituted)-amino-3-arylpyrrolinones of the general formula (I) haveherbicidal properties.

Surprisingly, the 4-(substituted)-amino-3-arylpyrrolinones of thegeneral formula (I) according to the invention show an outstandingherbicidal activity combined with an excellent tolerance by importantcrop plants.

Preferred compounds of the formula (I) are those in which

X and Y independently of one another are hydrogen, fluorine, chlorine,bromine, iodine, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₁ -C₆ -alkylthio, C₁-C₆ -halogenoalkoxy. halogeno-C₁ -C₄ -alkyl, or a radical from theseries comprising phenyl, phenoxy or phenylthio, each of which isunsubstituted or monosubstituted to penta-substituted by identical ordifferent substituents, the following being selected as phenylsubstituents: fluorine, chlorine, bromine, iodine, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy and halogeno-C₁ -C₄ -alkyl,

Z represents fluorine, chlorine, bromine, iodine, C₁ -C₆ -alkyl or C₁-C₆ -alkoxy,

n represents a number 0, 1, 2 or 3,

A represents a radical from the series comprising C₁ -C₁₂ -alkyl, C₃ -C₈-alkenyl, C₃ -C₈ -alkinyl, halogeno-C₁ -C₈ -alkyl, C₁ -C₁₀ -alkoxy-C₂-C₈ -alkyl, C₁ -C₈ -polyalkoxy-C₁ -C₈ -alkyl, C₁ -C₁₀ -alkylthio-C₁ -C₈-alkyl, each of which is unsubstituted or each of which is substitutedby halogen, or represents cycloalkyl which has 3 to 8 ring atoms andwhich can be interrupted by oxygen, nitrogen and/or sulphur, or Arepresents a radical from the series comprising phenyl-C₁ - C₆ -alkyl,phenyl or naphthyl, each of which is unsubstituted or monosubstituted topentasubstituted in the phenyl moiety by identical or differentsubstituents, selected substituents in each case being: fluorine,chlorine, bromine, iodine, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogeno-C₁-C₆ -alkyl, halogeno-C₁ -C₆ -alkoxy, or phenoxy or phenylthio, each ofwhich is unsubstituted or monosubstituted to pentasubstituted byidentical or different substituents from the series comprising fluorine,chlorine, bromine, iodine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogeno-C₁-C₄ -alkyl and halogeno-C₁ -C₄ -alkoxy,

B represents hydrogen, the group ##STR13## or the group ##STR14## Lrepresents hydrogen, or represents an optionally halogen-substitutedstraight-chain or branched radical from the series comprising C₁ -C₁₂-alkyl, C₃ -C₈ -alkenyl, C₃ -C₈ -alkinyl, C₁ -C₁₀ -alkoxy-C₂ -C₈ alkyl,C₁ -C₈ -polyalkoxy-C₂ -C₈ -alkyl, C₁ -C₁₀ alkylthio-C₂ -C₈ -alkyl,cycloalkyl which has 3-8 ring atoms and which can be interrupted byoxygen and/or sulphur, or represents a radical from the seriescomprising aryl, hetaryl or aryl-C₁ -C₆ -alkyl, each of which isoptionally substituted by halogen, C₁ -C₆ -alkyl-C₁ -C₆ -halogenoalkyl,C₁ -C₆ -alkoxy or nitro,

M represents hydrogen or a straight-chain or branched radical from theseries comprising C₁ -C₁₂ -alkyl, C₁ -C₈ -alkoxyalkyl,

or in which

A and L or L and M together with the atoms to which they are bonded forma 3 to 8-membered ring which can be saturated or unsaturated andsubstituted and/or interrupted by oxygen/sulphur,

R represents an optionally halogen-substituted straight-chain orbranched radical from the series comprising C₁ -C₁₂ -alkyl, C₃ -C₈-alkenyl, C₃ -C₈ -alkinyl, C₁ -C₁₀ -alkoxy-C₂ -C₈ -alkyl , C₁ -C₈-polyalkoxy-C₂ -C₈ -alkyl, C₁ -C₁₀ -alkylthio-C₂ -C₈ -alkyl, cycloalkylwhich has 3-8 ring atoms and which can be interrupted by oxygen and/orsulphur, or represents aryl which is optionally substituted by halogen,C₁ -C₆ -alkyl-C₁ -C₆ -halogenoalkyl, C₁ -C₆ -alkoxy or nitro,

and the enantiomeric forms of compounds of the formula (I) with theexception of the compounds:4-amino-1-cyclopropyl-3-(3-trifluoromethylphenyl)-3-pyrrolin-2-one and4-amino-1-isopropyl-3-(3-trifluoromethylphenyl)-3-pyrrolin-2-one.

A particularly preferred group of compounds of the formula (I) are thosein which

X represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n- oriso-propyl, methoxy, ethoxy, n- or i-propoxy, halogenomethyl having 1, 2or 3 fluorine and/or chlorine atoms, halogenoethyl having 1 to 5, inparticular 1 to 3, fluorine and/or chlorine atoms, C₁ -C₃-halogenoalkoxy, C₁ -C₃ -alkylthio, or phenyl, phenoxy or phenylthio,each of which is unsubstituted or monosubstituted to penta-substituted,in particular monosubstituted to tri-substituted, by identical ordifferent substituents, the following being selected as phenylsubstituents: fluorine, chlorine, bromine, methyl, ethyl, n- oriso-propyl, methoxy, ethoxy, n- or iso-propoxy and trifluoromethyl,

Y represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl,methoxy, ethoxy, trifluoromethoxy or trifluoromethyl,

Z represents fluorine or chlorine,

n represents 0, 1, 2 or 3 and

A represents methyl, ethyl, an in each case straight-chain or branchedradical from the series comprising propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, halogeno-C₁ -C₆ -alkyl , C₃ -C₆ -alkenyl, C₃ -C₆-alkinyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio-C₁ -C₄ -alkyl,or represents cycloalkyl which has 3 to 6 ring atoms and which can beinterrupted by oxygen, nitrogen or sulphur, or A represents a radicalfrom the series comprising phenyl, benzyl or phenethyl, each of which isunsubstituted or mono-substituted to pentasubstituted, in particularmonosubstituted to trisubstituted, by identical or differentsubstituents, selected substituents in each case being: fluorine,chlorine, methyl, ethyl, n- or iso-propyl, methoxy, ethoxy,trifluoromethyl, trifluoromethoxy, or phenoxy or phenylthio, each ofwhich is unsubstituted or monosubstituted to tri-substituted byidentical or different substituents from the series comprising fluorine,chlorine, methyl, methoxy, trifluoromethyl and trifluoromethoxy,

B represents hydrogen, the group ##STR15## or the group ##STR16## Lrepresents hydrogen, or represents an optionally halogen-substitutedstraight-chain or branched radical from the series comprising C₁ -C₁₀-alkyl, C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, C₁ -C₈ -alkoxy-C₂ -C₆ -alkyl,C₁ -C₆ -polyalkoxy-C₂ -C₆ -alkyl , C₁ -C₈ alkylthio-C₂ -C₆ -alkyl,cycloalkyl which has 3 to 7 ring atoms and which can be interrupted by 1to 2 oxygen and/or sulphur atoms, or aryl which is optionallysubstituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄ -halogenoalkyl, C₁ -C₄-alkoxy or nitro,

M represents hydrogen or a straight-chain or branched radical from theseries comprising C₁ -C₁₀ -alkyl, C₁ -C₆ -alkoxyalkyl,

or in which

A and L or L and M together with the atoms to which they are bonded forma 3 to 7-membered ring which can be saturated or unsaturated andsubstituted by C₁ -C₆ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₂ -halogenoalkyl orphenyl and/or interrupted by oxygen/sulphur,

R represents an optionally halogen-substituted straight-chain orbranched radical from the series comprising C₁ -C₁₀ -alkyl, C₃ -C₆-alkenyl, C₃ -C₆ -alkinyl, C₁ -C₈ -alkoxy-C₁ -C₆ -alkyl, C₁ -C₆-polyalkoxy-C₂ -C₆ -alkyl, C₁ -C₈ -alkylthio-C₂ -C₆ -alkyl, cycloalkylwhich has 3 to 7 ring atoms and which can be interrupted by 1 to 2oxygen and/or sulphur atoms, or represents aryl which is optionallysubstituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ -halogenoalkyl, C₁ -C₄-alkoxy or nitro,

and the enantiomeric compounds of the formula with the exception of thecompounds:4-amino-1-cyclopropyl-3-(3-trifluoromethylphenyl)-3-pyrrolin-2-one and4-amino-1-isopropyl-3-(3-trifluoromethylphenyl)-3-pyrrolin-2-one.

A very particularly preferred group of compounds are those of theformula (I) in which

X represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl,methoxy, ethoxy, n- or i-propoxy, trifluoromethyl, trifluoromethoxy, orrepresents phenyl or phenoxy, each of which is unsubstituted ormonosubstituted to trisubstituted by identical or differentsubstituents, selected substituents being the following: fluorine,chlorine, methyl and trifluoromethyl,

Y represents hydrogen, fluorine, chlorine, bromine, methyl, methoxy,trifluoromethoxy or trifluoromethyl,

n represents 0 and

A represents methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec.- ortert.-butyl, or represents an in each case straight-chain or branchedradical from the series comprising pentyl, hexyl, heptyl, octyl,halogeno-C₁ -C₃ -alkyl, allyl, propargyl, methoxymethyl, methoxyethyl,ethoxymethyl, ethoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl, orrepresents phenyl or benzyl, each of which is unsubstituted ormonosubstituted to trisubstituted by identical or different substituentsfrom the series comprising fluorine, chlorine, trifluoromethyl, phenoxyand 4-trifluoromethyl-phenoxy,

B represents hydrogen, the group --CO--R or the group ##STR17## Lrepresents hydrogen or an optionally halogen-substituted straight-chainor branched radical from the series comprising C₁ -C₈ -alkyl, C₃ -C₄-alkenyl, C₃ -C₄ alkinyl, C₁ -C₆ -alkoxy-C₂ -C₄ -alkyl, C₁ -C₄-polyalkoxy-C₂ -C₄ -alkyl, C₁ -C₆ -alkylthio-C₂ -C₄ -alkyl, cycloalkylwhich has 3 to 6 ring atoms and which can be interrupted by 1 to 2oxygen and/or sulphur atoms, or aryl which is optionally substituted byfluorine, chlorine, bromine, methyl, ethyl, propyl, iso-propyl, methoxy,ethoxy, trifluoromethyl or nitro,

M represents hydrogen or a straight-chain or branched radical from theseries comprising C₁ -C₈ -alkyl, C₁ -C₄ -alkoxyalkyl,

or in which

A and L or L and M together with the atoms to which they are bonded forma 3 to 6-membered ring which can be saturated or monounsaturated,substituted by C₁ -C₄ -alkyl, C₁ -C₂ -alkoxy, trifluoromethyl or phenyl,and/or interrupted by oxygen/sulphur,

R represents an optionally halogen-substituted straight-chain orbranched radical from the series comprising C₁ -C₈ -alkyl, C₃ -C₄-alkenyl, C₃ -C₄ -alkinyl, C₁ -C₆ -alkoxy-C₂ -C₄ -alkyl, C₁ -C₄-polyalkoxy-C₂ -C₄ -alkyl, C₁ -C₆ -alkylthio-C₂ -C₄ -alkyl, cycloalkylwhich has 3 to 6 ring atoms and which can be interrupted by 1 to 2oxygen and/or sulphur atoms, or represents aryl which is optionallysubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl,isopropyl, methoxy, ethoxy, trifluoromethyl or nitro,

and the enantiomeric compounds of the formula (I) with the exception ofthe compounds:4-amino-1-cyclopropyl-3-(3-trifluoromethylphenyl)-3-pyrrolin-2-one and4-amino-1-isopropyl-3-(3-trifluoromethylphenyl)-3-pyrrolin-2-one.

If, according to the general preparation process (aα),3-(3-trifluoromethylphenyl)-1-isopropyl-5-methylpyrrolidine-2,4-dioneand ammonium acetate are used as starting materials, the course of theprocess according to the invention can be represented by the followingequation: ##STR18##

If, according to the general preparation process (aβ),N-(3-trifluoromethylphenylacetyl)-N-methylamino-2-ethylacetonitrile isused, the course of the process according to the invention can berepresented by the following equation: ##STR19##

If, according to the general preparation process (bα),3-(3,4-dichlorophenyl)-1-(4-chlorophenyl)-4-amino-3-pyrrolin-2-one andacetyl chloride are used as starting materials, the course of theprocess according to the invention can be represented by the followingequation: ##STR20##

If, according to the general preparation process (bβ),3-(3-methoxyphenyl)-1-phenyl-5-methyl-4-amino-3-pyrrolin- 2-one and2-ethyl-butyric anhydride are used as starting materials, the course ofthe process according to the invention can be represented by thefollowing equation: ##STR21##

If, according to the general preparation process (c),3-(3-trifluoromethylphenyl)-1-tert.-butyl-5-methyl-4-amino-3-pyrrolin-2-oneand methyl chloroformate are used as starting materials, the course ofthe process according to the invention can be represented by thefollowing equation: ##STR22##

The compounds of the formula (II) ##STR23## in which A, L, M, X, Y, Zand n have the abovementioned meanings and which are required asstarting materials for carrying out process (aα) according to theinvention are obtained when N-acylamino acid esters of the formula (VII)##STR24## in which A, L, M, X, Y, Z and n have the abovementionedmeanings and

R¹ represents alkyl, in particular methyl or ethyl, are subjected tointramolecular condensation in the presence of a diluent and in thepresence of a base.

Some of the compounds of the formula (VII) are known or can be preparedin a simple manner by customary methods.

For example, N-acylamino acid esters of the formula (VII) are obtainedwhen acylamino acid esters of the formula (VIII) ##STR25## in which

R¹ represents hydrogen or alkyl, in particular methyl or ethyl, and

A, L and M have the abovementioned meanings, are acylated withphenylacetic acid halides of the formula (IX) ##STR26## in which Halrepresents halogen, in particular fluorine, chlorine or bromine, and

X, Y, Z and n have the abovementioned meanings, in the customary manner(cf. Chem. Rev. 52 (1953) 237-416 and Organikum [Laboratory Practical inOrganic Chemistry], 9th Edition, 446 (1970), VEB Deutscher Verlag derWissenschaften), or when N-acylamino acids of the formula (II) in whichR¹ represents hydrogen, are esterilied in the customary manner (cf.Chem. Ind. (London) 1568 (1968)).

Compounds of the formula (VII) in which R¹ represents hydrogen can alsobe prepared, for example, from phenylacetic acid halides of the formula(IX) and amino acids.

Compounds of the formula (VIII) can be obtained from α-halogenocarboxylic acids or α-halogeno carboxylates and amines or anilines,respectively, by processes known from the literature (Advanced OrganicChemistry, J. March, pp. 377, Mc Graw-Hill Inc. (1977)).

The phenylacetic acid halides of the formula (IX) are known compounds oforganic chemistry.

Some of the compounds of the formula (II) are compounds which are knownfrom EP-A-0,415,185. Compounds which were hitherto unknown are also partof the claim (see Table 1).

                                      TABLE 1                                     __________________________________________________________________________     ##STR27##                                                  (II)              Ex.                                                                           No.                                                                              X           Y           Z.sub.n                                                                         M  L            A                                __________________________________________________________________________    1  CF.sub.3    H           --                                                                              H  H                                                                                           ##STR28##                       2  CF.sub.3    H           --                                                                              CH.sub.3                                                                         H            CH.sub.2 CH.sub.2 OCH.sub.3      3  CF.sub.3    H           --                                                                              CH.sub.3                                                                         H            i-C.sub.3 H.sub.7                4  CF.sub.3    H           --                                                                              CH.sub.3                                                                         H            CH.sub.3                         5  H           H           --                                                                              CH.sub.3                                                                         H            i-C.sub.3 H.sub.7                6  CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR29##                       7  CF.sub.3    H           --                                                                              CH.sub.3                                                                         H            C.sub.2 H.sub.5                  8  CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR30##                       9  CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR31##                       10 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR32##                       11 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR33##                       12 CF.sub.3    H           --                                                                              H  CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2           13 H           Cl          --                                                                              H  CH.sub.2 SCH.sub.2 CH.sub.2                   14 H           Cl          --                                                                              H  CH.sub.2 SCH.sub.2                            15 H           Cl          --                                                                              H  CH.sub.2 CH.sub.2 SCH.sub.2                   16 Cl          Cl          --                                                                              H  CH.sub.3     CH.sub.3                         17 Cl          Cl          --                                                                              H  CH.sub.2 SCH.sub.2 CH.sub.2                   18 Cl          Cl          --                                                                              H  CH.sub.3     i-C.sub.3 H.sub.7                19 Cl          Cl          --                                                                              H  CH.sub.3                                                                                    ##STR34##                       20 Cl          Cl          --                                                                              H  C.sub.2 H.sub.5                                                                            CH.sub.3                         21 Cl          Cl          --                                                                              CH.sub.3                                                                         H                                                                                           ##STR35##                       22 Cl          Cl          --                                                                              CH.sub.3                                                                         H            C.sub.2 H.sub.5                  23 Cl          Cl          --                                                                              CH.sub.3                                                                         H            i-C.sub.4 H.sub.9                24 Br          H           --                                                                              CH.sub.3                                                                         H            CH.sub.3                         25 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H            C.sub.6 H.sub.5                  26 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR36##                       27 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR37##                       28 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR38##                       29 CF.sub.3    H           --                                                                              CF.sub.3                                                                         H                                                                                           ##STR39##                       30 H                                                                                          ##STR40##  --                                                                              H  CH.sub.3     C.sub.6 H.sub.5                  31                                                                                ##STR41##  H           --                                                                              H  CH.sub.3     C.sub.6 H.sub.5                  32 H           H           --                                                                              H  CH.sub.3                                                                                    ##STR42##                       33 CF.sub.3    Cl          --                                                                              H  (CH.sub.2).sub.4                              34 CF.sub.3    H           --                                                                              H  CH.sub.3     H.sub.3 COCH.sub.2 CHCH.sub.3    35 CF.sub.3    H           --                                                                              H                                                                                 ##STR43##   CH.sub.3                         36 CF.sub.3    H           --                                                                              H                                                                                 ##STR44##   CH.sub.3                         37 CF.sub.3    H           --                                                                              H                                                                                 ##STR45##   CH.sub.3                         38 CF.sub.3    H           --                                                                              H                                                                                 ##STR46##   CH.sub.3                         39 CF.sub.3    H           --                                                                              H                                                                                 ##STR47##   CH.sub.3                         40 CF.sub.3    H           --                                                                              H                                                                                 ##STR48##   CH.sub.3                         41 CF.sub.3    H           --                                                                              H  C.sub.6 H.sub.5                                                                            CH.sub.3                         42 CF.sub.3    H           --                                                                              H                                                                                 ##STR49##   CH.sub.3                         43 CF.sub.3    H           --                                                                              H                                                                                 ##STR50##   CH.sub.3                         44 CF.sub.3    H           --                                                                              H                                                                                 ##STR51##   CH.sub.3                         45 CF.sub.3    H           --                                                                              H                                                                                 ##STR52##   CH.sub.3                         46 CF.sub.3    H           --                                                                              H                                                                                 ##STR53##   CH.sub.3                         47 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H            CH.sub.2 -iPr                    48 CF.sub.3    H           --                                                                              H  C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                  49 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H            CH(CH.sub.3).sub.2               50 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H            C(CH.sub.3).sub.2 CH.sub.2                                                    C(CH.sub.3).sub.3                51 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR54##                       52 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR55##                       53 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H            CH.sub.2 CH.sub.2 OCH.sub.3      54 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR56##                       55 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR57##                       56 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR58##                       57 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR59##                       58 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR60##                       59 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR61##                       60 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR62##                       61 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR63##                       62 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR64##                       63 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H            CH.sub.2 C(CH.sub.3).sub.3       64 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H            CH(CH.sub.3)C(CH.sub.3).sub.3                                                 4                                65 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR65##                       66 H           H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR66##                       67 H           H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR67##                       68 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H            CH(CH.sub.3)CH(CH.sub.3).sub.                                                 2                                69 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR68##                       70                                                                                ##STR69##  H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR70##                       71 H                                                                                          ##STR71##  --                                                                              CH.sub.3                                                                         H                                                                                           ##STR72##                       72 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR73##                       73 H           H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR74##                       74 H           H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR75##                       75 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR76##                       76 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR77##                       77 H           H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR78##                       78 F           F           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR79##                       79 CF.sub.3    H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR80##                       80 Cl          Cl          --                                                                              CH.sub.3                                                                         H            CH.sub.2 CH(CH.sub.3).sub.2      81 Cl          Cl          --                                                                              CH.sub. 3                                                                        H                                                                                           ##STR81##                       82 Cl          Cl          --                                                                              CH.sub.3                                                                         H                                                                                           ##STR82##                       83 Cl          Cl          --                                                                              CH.sub.3                                                                         H                                                                                           ##STR83##                       84 Cl          Cl          --                                                                              CH.sub.3                                                                         H            CH.sub.2 CH.sub.2 OCH.sub.3      85 Cl          Cl          --                                                                              CH.sub.3                                                                         H            CH(CH.sub.3).sub.2               86 Cl          Cl          --                                                                              CH.sub.3                                                                         H            CH.sub.3                         87 Br          H           --                                                                              CH.sub.3                                                                         H            CH.sub.2 CH(CH.sub.3).sub.2      88 Br          H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR84##                       89 Br          H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR85##                       90 Br          H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR86##                       91 Br          H           --                                                                              CH.sub.3                                                                         H                                                                                           ##STR87##                       92 Br          H           --                                                                              CH.sub.3                                                                         H            CH.sub.2 CH.sub.2 OCH.sub.3      93 Br          H           --                                                                              CH.sub.3                                                                         H            CH(CH.sub.3).sub.2               94 Br          H           --                                                                              CH.sub.3                                                                         H            C.sub.2 H.sub.5                  95 Br          H           --                                                                              CH.sub.3                                                                         H            CH.sub.3                         __________________________________________________________________________

The process for the preparation of compounds of the formula (II) ischaracterised in that compounds of the formula (VII) are subjected tointramolecular condensation in the presence of bases.

Diluents which can be employed in this process according to theinvention are all customary inert organic solvents. The following canpreferably be used: hydrocarbons such as toluene and xylene, furthermoreethers such as dibutyl ether, tetrahydrofuran, dioxane, glylcol dimethylether and diglycol dimethyl ether, moreover polar solvents such asdimethyl sulphoxide, sulpholane, dimethylformamide,N-methyl-pyrrolidone, and also alcohols such as ethanol, methanol,isobutanol, sec.-butanol and tert.-butanol.

Deprotonating agents which can be employed for carrying out this processaccording to the invention are all customary proton acceptors. Thefollowing can preferably be used: the oxides, hydroxides and carbonatesof alkali metals and alkaline earth metals such as sodium hydroxide,potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate,potassium carbonate and calcium carbonate, all of which can also beemployed in the presence of phase transfer catalysts such as, forexample, triethylbenzylammonium chloride, tetrabutylammonium bromide,*Adogen 464 or TDA 1. Other substances which can be employed are amidesand hydrides of alkali metals and alkaline earth metals such as sodiumamide, sodium hydride and calcium hydride, and moreover also alkalimetal alcoholates such as sodium methylate and potassium tert.-butylate.

When carrying out this process according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

The process according to the invention is generally carried out underatmospheric pressure.

When carrying out this process according to the invention, the reactantsof the formula (VII) and the deprotonating bases are generally employedin approximately equimolar amounts. However, it is also possible to useone or the other component in a larger excess (up to 3 moles).

Diluents which are preferably suitable for carrying out process (aα)according to the invention are inert organic solvents. These include, inparticular, aliphatic, alicyclic or aromatic, optionally halogenatedhydrocarbons such as, for example, benzine, ligroine, benzene, toluene,xylene, chlorobenzene, petroleum ether, pentane, hexane, heptane,cyclohexane, dichloromethane, chloroform, carbon tetrachloride, etherssuch as diethyl ether, dioxane, tetrahydrofuran or ethylene glycoldimethyl ether or ethylene glycol diethyl ether, ketones such as acetoneor butanone, nitriles such as acetonitrile or propionitrile, amides,such as dimethylformamide, dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide, or esters, such asethyl acetate. A suitable excess of the amines of the formula (IV) inliquid form can also be employed as solvent.

If appropriate, process (aα) according to the invention is carried outin the presence of a dehydrating agent. The following are preferablyused as dehydrating agents:

molecular sieves or catalytic amounts of, for example,p-toluenesulphonic acid. A favourable procedure is removal of the waterduring the reaction by azeotropic distillation.

When carrying out process (aα) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 300° C.,preferably at temperatures between 20° C. and 250° C.

Process (aα) according to the invention is customarily carried out underatmospheric pressure. However, the process can also be carried out underincreased pressure.

For carrying out process (aα) according to the invention, 1 to 30 moles,preferably 1 to 10 moles, of ammonia or an ammonium salt and, ifappropriate, 1 to 5 moles of dehydrating agent are generally employedper mole of compound of the formula (II) in which B represents hydroxyl.The reaction is carried out and the reaction products are worked up andisolated analogously to generally known processes.

Process (aα) is characterised in that compounds of the formula (III) aresubjected to intramolecular condensation in the presence of bases.

Diluents which can be employed in process (aβ) according to theinvention are all customary inert organic solvents. The following canpreferably be used: hydrocarbons such as toluene and xylene, furthermoreethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethylether and diglycol dimethyl ether, moreover polar solvents such asdimethyl sulphoxide, sulpholane, dimethylformamide,N-methyl-pyrrolidone, and also alcohols such as ethanol, methanol,isobutanol, sec.-butanol and tert.-butanol.

Deprotonating agents which can be employed for carrying out process (aβ)according to the invention are all customary proton acceptors. Thefollowing can preferably be used: the oxides, hydroxides and carbonatesof alkali metals and alkaline earth metals such as sodium hydroxide,potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate,potassium carbonate and calcium carbonate, all of which can also beemployed in the presence of phase transfer catalysts such as, forexample, triethylbenzylammonium chloride, tetrabutylammonium bromide,*Adogen 464 or TDA 1. Other substances which can be employed are amidesand hydrides of alkali metals and alkaline earth metals such as sodiumamide, sodium hydride and calcium hydride, and moreover also alkalimetal alcoholates such as sodium methylate and potassium tert.-butylate.

When carrying out process (aβ) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

The process (aβ) is generally carried out under atmospheric pressure.

When carrying out process (aβ), the reactants of the formula (III) andthe deprotonating bases are generally employed in approximatelyequimolar amounts. However, it is also possible to use one or the othercomponent in a larger excess (up to 3 moles).

Process (bα) is characterised in that compounds of the formula (Ia) arereacted with carboxylic acid halides of the formula (IV).

When the acid halides are used, then diluents which can be employed inprocess (bα) according to the invention are all solvents which are inertto these compounds. The following can preferably be used: hydrocarbonssuch as benzine, benzene, toluene, xylene and tetraline, furthermorehalogeno hydrocarbons such as methylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketonessuch as acetone and methyl isopropyl ketone, furthermore ethers such asdiethyl ether, tetrahydrofuran and dioxane, and additionallysulphoxides, such as dimethyl sulphoxide and sulpholane. If stability tohydrolysis of the acid halide permits, the reaction can also be carriedout in the presence of water. However, it is also possible to carry outthe process without solvent.

If the corresponding carboxylic acid halides are used, then suitableacid-binding agents in the reaction by process (bα) according to theinvention are all customary acid acceptors. The following can preferablybe used: tertiary amines such as triethylamine, pyridine,diazabicyclooctane (DABCO), diazabicycloundecene (DBU),diazabicyclononene (DBN), Hunig base and N,N-dimethylaniline,furthermore alkaline earth metal oxides such as magnesium oxide andcalcium oxide, moreover alkali metal carbonates and alkaline earth metalcarbonates such as sodium carbonate, potassium carbonate and calciumcarbonate. However, acid-binding agents can also be dispensed with.

The reaction temperatures in process (aα) according to the invention canbe varied within a substantial range, even when carboxylic acid halidesare used. The process is generally carried out at temperatures between-20° C. and +200° C., preferably between 0° C. and 150° C.

When carrying out process (bα) according to the invention, the startingmaterials of the formula (Ia) and the carboxylic acid halide of theformula (IV) are generally employed in approximately equivalent amounts.However, it is also possible to employ the carboxylic acid chloride in alarger excess (up to 20 moles). Working-up is carried out by customarymethods.

Process (bβ) is characterised in that compounds of the formula (Ia) arereacted with carboxylic acid hydrides of the formula (V).

If carboxylic anhydrides are used as reactant of the formula (V) inprocess (bβ) according to the invention, then the diluents which arepreferably used are those which are also preferably suitable when acidhalides are used. Besides, an excess of carboxylic acid hydride can alsoact simultaneously as the diluent.

The reaction temperatures in process (bβ) according to the invention canbe varied within a substantial range, even when carboxylic anhydridesare used. In general, the process is carried out at temperatures between-20° C. and 200° C., preferably between 0° C. and 150° C.

When carrying out process (bβ) according to the invention, the startingmaterials of the formula (Ia) and the carboxylic anhydride of theformula (V) are generally employed in approximately equivalent amounts.However, it is also possible to employ the carboxylic anhydride in alarger excess (up to 20 moles). Working-up is carried out by customarymethods.

In general, a procedure is followed in which diluents and excesscarboxylic anhydride and the carboxylic acid which forms are removed bydistillation or by washing with an organic solvent or with water.

Process (c) is characterised in that compounds of the formula (Ia) arereacted with chloroformates of the formula (VI).

If the corresponding chloroformates are used, then suitable acid-bindingagents in the reaction by process (c) according to the invention are allcustomary acid acceptors. The following can preferably be used: tertiaryamines such as triethylamine, pyridine, DABCO, DBU, DBN, Hunig base andN,N-dimethyl-aniline, furthermore alkaline earth metal oxides such asmagnesium oxide and calcium oxide, moreover alkali metal carbonates andalkaline earth metal carbonates such as sodium carbonate, potassiumcarbonate and calcium carbonate.

When the chloroformates are used, then diluents which can be employed inprocess (c) according to the invention are all solvents which are inertto these compounds. The following can preferably be used: hydrocarbonssuch as benzine, benzene, toluene, xylene and tetraline, furthermorehalogeno hydrocarbons such as methylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketonessuch as acetone and methyl isopropyl ketone, furthermore ethers such asdiethyl ether, tetrahydrofuran and dioxane, in addition carboxylatessuch as ethyl acetate, and also strongly polar solvents such as dimethylsulphoxide and sulpholane. However, the process can also be carried outwithout solvent.

When the chloroformates are used as carboxylic acid derivatives of theformula (VI), the reaction temperatures for carrying out process (c)according to the invention can be varied within a substantial range. Ifthe process is carried out in the presence of a diluent and of anacid-binding agent, then the reaction temperatures are generally between-20° C. and +250° C., preferably between 0° C. and 150° C.

Process (c) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (c) according to the invention, the startingmaterials of the formula (Ia) and the corresponding chloroformate of theformula (VI) are generally used in approximately equivalent amounts.However, it is also possible to employ one or the other component in alarger excess (up to 10 moles). Working-up is then carried out bycustomary methods. In general, a procedure is followed in whichprecipitated salts are removed and the reaction mixture which remains isconcentrated by removing the diluent in vacuo.

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,especially, as weed-killers. By weeds, in the broadest sense, there areto be understood all plants which grow in locations where they areundesired. Whether the substances according to the invention act astotal or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the qenera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants. The compounds are suitable, depending on theconcentration, for the total combating of weeds, for example onindustrial plants and railway lines, and on paths and squares with orwithout tree plantings. Equally, the compounds can be employed forcombating weeds in perennial cultures, for example afforestations,decorative tree plantings, orchards, vineyards, citrus groves, nutorchards, banana plantations, coffee plantations, tea plantations,rubber plantations, oil palm plantations, cocoa plantations, soft fruitplantings and hopfields, in lawns, turf and pasture-land, and for theselective combating of weeds in annual cultures.

The active compounds according to the invention are very suitable forthe selective combating of mono- and dicotyledon weeds in mono- anddicotyledon crops in the pre- and post-emergence method.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene, oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates, assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,maize cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example nonionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumen hydrolysis products; asdispersing agents there are suitable: for example lignin-sulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the forth of powders, granules or latexes, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedye-stuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

For combating weeds, the active compounds according to the invention, assuch or in the form of their formulations, can also be used as a mixturewith known herbicides, finished formulations or tank mixes beingpossible.

Suitable herbicides for the mixtures are known herbicides, for exampleanilides such as, for example, diflufenican and propanil; arylcarboxylicacids such as, for example, dichloropicolinic acid, dicamba andpicloram; aryloxyalkanoic acids such as, for example, 2,4 D, 2,4 DB, 2,4DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoicesters such as, for example, diclofop-methyl, fenoxaprop-ethyl,fluazifopbutyl, haloxyfop-methyl and quizalofop-ethyl; azinones such as,for example, chloridazon and norflurazon; carbamates such as, forexample, chlorpropham, desmedipham, phenmediphamand propham;chloroacetanilides such as, for example, alachlor, acetochlor,butachlor, metazachlor, metolachlor, pretilachlor and propachlor;dinitroanilines such as, for example, oryzalin, pendimethalin andtrifluralin; diphenyl ethers such as, for example, acifluorfen, bifenox,fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureassuch as, for example, chlortoluron, diuron, fluometuron, isoproturon,linuron and methabenzthiazuron; hydroxylamines such as, for example,alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim;imidazolinones such as, for example, imazethapyr, imazamethabenz,imazapyr and imazaquin; nitriles such as, for example, bromoxynil,dichlobenil and ioxynil; oxyacetamides such as, for example, mefenacet;sulphonylureas such as, for example, amidosulfuron, bensulfuron-methyl,chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl,nicosulfuron, primisulfuron, pyrazosulfuron-ethyl,thifensulfuron-methyl, triasulfuron and tribehuron-methyl;thiocarbanates such as, for example, butylate, cycloate, di-allate,EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and tri-allate;triazines such as, for example, atrazine, cyanazine, simazine, simetryn,terbutryn and terbutylazine; triazinones such as, for example,hexazinone, metamitron and metribuzin; others such as, for example,aminotriazol, benfuresate, bentazone, cinmethylin, clomazone,clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone,glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac,sulphosate and tridiphane.

A mixture with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellants, plant nutrientsand agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 0.01 and 15 kg of active compound perhectare of soil surface, preferably between 0.05 and 10 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES EXAMPLE 1

Synthesis of the acylamino acid ester (VIII) ##STR88##

22.2 g (0.2 mol) of 3-fluoroaniline were introduced into 100 ml ofxylene and 20.2 g (0.2 mol) of triethylamine are added. The mixture isthen cooled to 10°-20° C., during which process 33.4 g (0.2 mol) ofethyl bromoacetate is added dropwise. When this procedure has ended, themixture is refluxed for 8 hours and then allowed to cool, and the xyleneis removed in vacuo. The residue is treated with 100 ml of water, andthe mixture extracted twice using 60 ml portions of methylene chlorideand dried over magnesium sulphate. Finally, the magnesium sulphate isremoved by filtration, the solution is concentrated in vacuo, and 37.6 g(95.4% of theory) of 3-fluorophenylacylamino acid ethyl ester areobtained in the form of a yellow oil which is identified by NMRspectroscopy.

EXAMPLE 2

Synthesis of the N-acylamino acid esters (VII) ##STR89##

19.7 g (0.1 mol) of 3-fluorophenylacylamino acid ethyl ester and 10.1 g(0.1 mol) of triethylamine are introduced into 150 ml oftetrahydrofuran. The mixture is cooled to 2° to 6° C., and 22.3 g (0.1mol) of 3-trifluoromethylphenylacetic acid chloride in 20 m 1 oftetrahydrofuran are then added dropwise.

When the procedure has ended, stirring of the mixture is continued for30 minutes at room temperature, the reaction solution is introduced into700 ml of ice-water, the mixture is treated with 100 ml of 1-normal HCland extracted twice using 150 ml portions of methylene chloride, and thecombined organic phases are dried over magnesium sulphate.

After the magnesium sulphate has been filtered off, the solvent isremoved in vacuo, and 37 g (96.6% of theory) ofN-(3-fluorophenyl)-N-(3-trifluoromethylphenylacetyl)-acylamino acidethyl ester, which is identified by NMR spectroscopy, are obtained.

EXAMPLE 3

Synthesis of the intermediates (II) ##STR90## 3.77 g (0.126 mol) ofsodium hydride are introduced into 90 ml of absolute toluene, and 37 g(0.097 mol) ofN-(3-fluorophenyl)-N-(3-trifluoromethylphenylacetyl)-acylamino acidethyl ester, also dissolved in 100 ml of absolute toluene, are addeddropwise at 90° C. to 100° C. The mixture is subsequently refluxed forone hour after the reaction, before being cooled to 3° C. to 5° C.(ice-bath mixture) and 30 ml of ethanol, 75 ml of water and 20 ml ofconcentrated hydrochloric acid are added dropwise. The white precipitatewhich separates out during this process is finally filtered off, washedwith acetone and dried.

27.2 g (83.4% of theory) of 3-(3-trifluoromethylphenyl)-1-(3-fluorophenyl)-pyrrolidine-2,4-dione of melting point 208° C. to209° C., which is identified by NMR spectroscopy, are obtained.

The products of the formula (II) which are subsequently listed in Table2 are obtained analogously to the above-described synthesis of theintermediates (II) and taking into consideration the information in thedescription of process (a) according to the invention.

                                      TABLE 2                                     __________________________________________________________________________     ##STR91##                                                  (II)              __________________________________________________________________________    Ex. No.                                                                              X     Y     Z    n    M     L     A            Melting                                                                       point/°C.        __________________________________________________________________________    II-2   CF.sub.3                                                                            H     --   --   CH.sub.3                                                                            H     CH.sub.2 CH.sub.2 OCH.sub.3                                                                138                     II-3   CF.sub.3                                                                            H     --   --   CH.sub.3                                                                            H     i-C.sub.3 H.sub.7                                                                          189                     II-4   CF.sub.3                                                                            H     --   --   CH.sub.3                                                                            H     CH.sub.3     207                     II-5   H     H     --   --   CH.sub.3                                                                            H     i-C.sub.3 H.sub.7                                                                          180                     II-6   H     H     --   --   CH.sub.3                                                                            H                                                                                    ##STR92##   207                     II-7   CF.sub.3                                                                            H     --   --   CH.sub.3                                                                            H     C.sub.2 H.sub.5                                                                            205                     II-8   CF.sub.3                                                                            H     --   --   CH.sub.3                                                                            H                                                                                    ##STR93##   218                     II-9   CF.sub.3                                                                            H     --   --   CH.sub.3                                                                            H                                                                                    ##STR94##   191                     II-10  CF.sub.3                                                                            H     --   --   CH.sub.3                                                                            H                                                                                    ##STR95##   168                     II-11  CF.sub.3                                                                            H     --   --   CH.sub.3                                                                            H                                                                                    ##STR96##   218                     II-12  CF.sub.3                                                                            H     --   --   H     CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                              >220                    II-13  H     Cl    --   --   H     CH.sub.2 SCH.sub.2 CH.sub.2                                                                      230                     II-14  H     Cl    --   --   H     CH.sub.2 SCH.sub.2 183                     II-15  H     Cl    --   --   H     CH.sub.2 CH.sub.2 SCH.sub.2                                                                      230                     II-16  Cl    Cl    --   --   H     CH.sub.3                                                                            CH.sub.3     233                     II-17  Cl    Cl    --   --   H     CH.sub.2 SCH.sub.2 CH.sub.2                                                                      230                     II-18  Cl    Cl    --   --   H     CH.sub.3                                                                            i-C.sub.3 H.sub.7                                                                          202                     II-19  Cl    Cl    --   --   H     CH.sub.3                                                                             ##STR97##   >220                    II-20  Cl    Cl    --   --   H     C.sub.2 H.sub.5                                                                     CH.sub.3     220                     __________________________________________________________________________    Ex. No. X     Y    Z    n    L    M     A           Melting                                                                       point/°C.          __________________________________________________________________________    II-21   Cl    Cl   --   --   H    CH.sub.3                                                                             ##STR98##  >220                      II-22   Cl    Cl   --   --   H    CH.sub.3                                                                            C.sub.2 H.sub.5                                                                           200                       II-23   Cl    Cl   --   --   H    CH.sub.3                                                                            i-C.sub.4 H.sub.9                                                                         196                       II-24   Br    H    --   --   H    CH.sub.3                                                                            CH.sub.3    201                       II-25   CF.sub.3                                                                            H    --   --   H    CH.sub.3                                                                            C.sub.6 H.sub.5                                                                           216                       II-26   CF.sub.3                                                                            H    --   --   H    CH.sub.3                                                                             ##STR99##  112                       II-27   CF.sub.3                                                                            H    --   --   H    CH.sub.3                                                                             ##STR100## 201                       II-28   CF.sub.3                                                                            H    --   --   H    CH.sub.3                                                                             ##STR101## 195                       __________________________________________________________________________    Ex.                                                       Melting             No.                                                                              X           Y           Z.sub.n                                                                          L M            A            point/°C.    __________________________________________________________________________    II-29                                                                            CF.sub.3    H           -- H CH.sub.3                                                                                    ##STR102##  216-217             II-30                                                                            H                                                                                          ##STR103## -- H CH.sub.3     C.sub.6 H.sub.5                                                                            249                 II-31                                                                             ##STR104## H           -- H CH.sub.3     C.sub.6 H.sub.5                                                                             77                 II-32                                                                            H           H           -- H CH.sub.3                                                                                    ##STR105##  239-240             II-33                                                                            CF.sub.3    Cl          -- H (CH.sub.2).sub.4          244                 II-34                                                                            CF.sub.3    H           -- H  CH.sub.3    H.sub.3 COCH.sub.2 CHCH.sub.3                                                              210                 II-35                                                                            CF.sub.3    H           -- H                                                                                ##STR106##  CH.sub.3     154-156             II-36                                                                            CF.sub.3    H           -- H                                                                                ##STR107##  CH.sub.3     148-150             II-37                                                                            CF.sub.3    H           -- H                                                                                ##STR108##  CH.sub.3     183-185             II-38                                                                            CF.sub.3    H           -- H                                                                                ##STR109##  CH.sub.3     138-140             II-39                                                                            CF.sub.3    H           -- H                                                                                ##STR110##  CH.sub.3     123-125             II-40                                                                            CF.sub.3    H           -- H                                                                                ##STR111##  CH.sub.3     139-141             II-41                                                                            CF.sub.3    H           -- H C.sub.6 H.sub.5                                                                            CH.sub.3     216-218             II-42                                                                            CF.sub.3    H           -- H                                                                                ##STR112##  CH.sub.3     176-178             II-43                                                                            CF.sub.3    H           -- H                                                                                ##STR113##  CH.sub.3     221-223             II-44                                                                            CF.sub.3    H           -- H                                                                                ##STR114##  CH.sub.3     237-239             __________________________________________________________________________    Ex. No.                                                                            X           Y   Z.sub.n                                                                          M   L           A             Melting                                                                       point/°C.        __________________________________________________________________________    II-45                                                                              CF.sub.3    H   -- H                                                                                  ##STR115## CH.sub.3      204-206                 II-46                                                                              CF.sub.3    H   -- H                                                                                  ##STR116## CH.sub.3      200-203                 II-47                                                                              CF.sub.3    H   -- CH.sub.3                                                                          H           CH.sub.2 -iPr 178                     II-48                                                                              CF.sub.3    H   -- H   C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                             168                     II-49                                                                              H           H   -- H   H                                                                                          ##STR117##   250                     II-50                                                                              CF.sub.3    H   -- H   H                                                                                          ##STR118##   223                     II-51                                                                              CF.sub.3    H   -- H   H                                                                                          ##STR119##   248                     II-52                                                                              CF.sub.3    H   -- H   H                                                                                          ##STR120##   250                     II-53                                                                              H           CH.sub.3                                                                          -- H   H                                                                                          ##STR121##   250                     II-54                                                                              H           F   -- H   H                                                                                          ##STR122##   250                     II-55                                                                              H           F   -- H   H                                                                                          ##STR123##   250                     II-56                                                                              F           H   -- H   H                                                                                          ##STR124##   248                     II-57                                                                              F           H   -- H   H                                                                                          ##STR125##   248                     II-58                                                                              F           H   -- H   H                                                                                          ##STR126##   247                     II-59                                                                              F           H   -- H   H                                                                                          ##STR127##   235                     II-60                                                                              CF.sub.3    H   -- H   H           C.sub.3 H.sub.7 iso                                                                         210                     II-61                                                                               ##STR128## H   -- H   H                                                                                          ##STR129##   205-206                 II-62                                                                               ##STR130## H   -- H   H                                                                                          ##STR131##   226                     I-63 H           H   -- H   H                                                                                          ##STR132##   230-232                 I-64 CF.sub.3    H   -- CH.sub.3                                                                          H                                                                                          ##STR133##   208-209                 I-65 Cl          H   -- H   H                                                                                          ##STR134##   235                     I-66 Cl          H   -- H   H                                                                                          ##STR135##   243                     I-67 Cl          H   -- H   H                                                                                          ##STR136##   250                     I-68 Cl          Cl  -- H   H                                                                                          ##STR137##   265-270                 I-69 CF.sub.3    H   -- CH.sub.3                                                                          H           CH.sub.2 CH.sub.2 OCH.sub.3                                                                 123-124                 I-70 CF.sub.3    H   -- CH.sub.3                                                                          H                                                                                          ##STR138##   189-191                 I-71 CF.sub.3    H   -- CH.sub.3                                                                          H                                                                                          ##STR139##   123-125                 I-72 CF.sub.3    H   -- H   H           CH.sub.2 CH.sub.2 SCH.sub. 2                                                                224-226                 I-73 CF.sub.3    H   -- H   CH.sub.2 CH.sub.2 CH.sub.2                                                                              234-236                 I-74 CF.sub.3    H   -- CH.sub.3                                                                          H           CH.sub.2 C(CH.sub.3).sub.3                                                                  215-218                 I-75 CF.sub.3    H   -- H                                                                                  ##STR140##               267-270                 I-76 CF.sub.3    H   -- --  --                                                                                         ##STR141##   215-217                 __________________________________________________________________________

EXAMPLE 4

Synthesis of the 4-amino-3-arylpyrrolinone derivatives of the formula(Ia) ##STR142##

Process aα

3.77 g (0.01 mol) of3-(3-trifluoromethylphenyl)-1-(3-fluorophenyl)-pyrrolidine-2,4-dione(II-1) are introduced into 80 ml of xylene, and the mixture is treatedwith 5 ml of glacial acetic acid and 2 ml of 25% strength aqueousammonia solution and subsequently refluxed for 6 hours in a waterseparator. After in each case 2 hours, another 5 ml of glacial aceticacid and 2 ml of ammonia solution are added, so that finally a total of15 ml of glacial acetic acid and 6 ml of ammonia solution were added.After the last addition, the mixture is refluxed for another hour in awater separator before removing the volatile components in vacuo. Theresidue is taken up in 50 ml of water, the mixture is extracted threetimes using 80 ml portions of methylene chloride, and the combinedorganic phases are washed once with water, dried over magnesium sulphateand concentrated in vacuo. The crystalline residue obtained during thisprocess is stirred with petroleum ether/methylene chloride (1:1), andthe white precipitate is filtered off.

3.2 g (73% of theory) of4-amino-l-(3-fluorophenyl)3-(3-trifluorophenyl)-pyrrolin-2-one ofmelting point 201°-203° C. are obtained.

The compound is identified by NMR and MS spectroscopy. In individualcases, the crude produce must be chromatographed over silica gel usingtoluene/acetone (1:1) as eluent, which may reduce the yields to 45 to75%.

The end products of the formula (Ia) in which B represents hydrogen andwhich are listed below in Table 3 are obtained analogously to Example 4and taking into consideration the information in the description ofprocess (a) according to the invention.

                                      TABLE 3                                     __________________________________________________________________________     ##STR143##                                                 (Ia)              Ex. No.                                                                            X           Y Z n M             L A             Melting                                                                       point/°C.         __________________________________________________________________________    Ia-2 CF.sub.3    H --                                                                              --                                                                              CH.sub.3      H CH.sub.3      130                      Ia-3 H           H --                                                                              --                                                                              CH.sub.3      H                                                                                ##STR144##   190                      Ia-4 H           H --                                                                              --                                                                              CH.sub.3      H i-C.sub.3 H.sub.7                                                                           170                      Ia-5 CF.sub.3    H --                                                                              --                                                                              H             H CH.sub.3      167                      Ia-6 CF.sub.3    H --                                                                              --                                                                              CH.sub.3      H C.sub.2 H.sub.5                                                                             180                      Ia-7 CF.sub.3    H --                                                                              --                                                                              C.sub.2 H.sub.5                                                                             H C.sub.2 H.sub.5                                                                             139                      Ia-8 CF.sub.3    H --                                                                              --                                                                              CH.sub.3      H i-C.sub.3 H.sub.7                                                                           173                      Ia-9 CF.sub.3    H --                                                                              --                                                                              CH.sub.3      H                                                                                ##STR145##   160                      Ia-10                                                                              CF.sub.3    H --                                                                              --                                                                              CH.sub.3      H i-C.sub.4 H.sub.9                                                                           173                      Ia-11                                                                              CF.sub.3    H --                                                                              --                                                                              CH.sub.3      H                                                                                ##STR146##   145                      Ia-12                                                                              CF.sub.3    H --                                                                              --                                                                              H             H                                                                                ##STR147##   236                      Ia-13                                                                              CF.sub.3    H --                                                                              --                                                                              CH.sub.3      H                                                                                ##STR148##   238-239                  Ia-14                                                                              CF.sub.3    H --                                                                              --                                                                              H             H                                                                                ##STR149##   185-186                  Ia-15                                                                               ##STR150## H --                                                                              --                                                                              H             H                                                                                ##STR151##   110                      Ia-16                                                                              CF.sub.3    H --                                                                              --                                                                              CH.sub.3      H                                                                                ##STR152##   143                      Ia-17                                                                              Cl          Cl                                                                              --                                                                              --                                                                              CH.sub.3      H CH.sub.3      194                      Ia-18                                                                              Cl          Cl                                                                              --                                                                              --                                                                              H             CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                           >220                     Ia-19                                                                              CF.sub.3    H --                                                                              --                                                                              H             CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                           180                      Ia-20                                                                              Cl          Cl                                                                              --                                                                              --                                                                              CH.sub.3      H                                                                                ##STR153##   165                      Ia-21                                                                              Cl          Cl                                                                              --                                                                              --                                                                              C.sub.2 H.sub.5                                                                             H CH.sub.3      178                      Ia-22                                                                              Cl          Cl                                                                              --                                                                              --                                                                              CH.sub.3      H                                                                                ##STR154##   188                      Ia-23                                                                              Cl          Cl                                                                              --                                                                              --                                                                              CH.sub.3      H i-C.sub.3 H.sub.7                                                                           >220                     Ia-24                                                                              Cl          Cl                                                                              --                                                                              --                                                                              CH.sub.3      H i-C.sub.4 H.sub.9                                                                           150                      Ia-25                                                                              Cl          Cl                                                                              --                                                                              --                                                                              CH.sub.3      H C.sub.2 H.sub.5                                                                             140                      Ia-26                                                                              Br          H --                                                                              --                                                                              CH.sub.3      H CH.sub. 3     198                      Ia-27                                                                              H           H --                                                                              --                                                                              H             H                                                                                ##STR155##   164                      Ia-28                                                                              H           H --                                                                              --                                                                              H             H                                                                                ##STR156##   161                      Ia-29                                                                              Cl          Cl                                                                              --                                                                              --                                                                               ##STR157##   H CH.sub.3      155-156                  Ia-30                                                                              Cl          Cl                                                                              --                                                                              --                                                                               ##STR158##   H CH.sub.3      145-150                  Ia-31                                                                              Cl          Cl                                                                              --                                                                              --                                                                               ##STR159##   H CH.sub.3      175-180                  Ia-32                                                                              Cl          Cl                                                                              --                                                                              --                                                                               ##STR160##   H CH.sub.3      195-200                  Ia-33                                                                              Cl          Cl                                                                              --                                                                              --                                                                               ##STR161##   H CH.sub.3      205-208                  Ia-34                                                                              Cl          Cl                                                                              --                                                                              --                                                                               ##STR162##   H CH.sub.3      225-230                  Ia-35                                                                              Cl          Cl                                                                              --                                                                              --                                                                               ##STR163##   H CH.sub.3      185-190                  Ia-36                                                                              Cl          Cl                                                                              --                                                                              --                                                                               ##STR164##   H CH.sub.3      210-215                  Ia-37                                                                              Cl          Cl                                                                              --                                                                              --                                                                               ##STR165##   H CH.sub.3      180-185                  Ia-38                                                                              Cl          Cl                                                                              --                                                                              --                                                                               ##STR166##   H CH.sub.3      183-184                  Ia-39                                                                              Cl          Cl                                                                              --                                                                              --                                                                              H             H                                                                                ##STR167##   260-262                  Ia-40                                                                              Cl          Cl                                                                              --                                                                              --                                                                               ##STR168##   H CH.sub.3      202-204                  Ia-41                                                                              Cl          H --                                                                              --                                                                              H             H                                                                                ##STR169##   Harz                     Ia-42                                                                              CF.sub.3    H --                                                                              --                                                                               ##STR170##   H CH.sub.3      135-7                    Ia-43                                                                              CF.sub.3    H --                                                                              --                                                                               ##STR171##   H CH.sub.3      168                      Ia-44                                                                              CF.sub.3    H --                                                                              --                                                                               ##STR172##   H CH.sub.3      142                      Ia-45                                                                              CF.sub.3    H --                                                                              --                                                                               ##STR173##   H CH.sub.3      160-2                    Ia-46                                                                              CF.sub.3    H --                                                                              --                                                                               ##STR174##   H CH.sub.3      170                      Ia-47                                                                              CF.sub.3    H --                                                                              --                                                                               ##STR175##   H CH.sub.3      50-3                     Ia-48                                                                              CF.sub.3    H --                                                                              --                                                                               ##STR176##   H CH.sub.3      122                      Ia-49                                                                              CF.sub.3    H --                                                                              --                                                                               ##STR177##   H CH.sub.3      140-2                    Ia-50                                                                              CF.sub.3    H --                                                                              --                                                                               ##STR178##   H CH.sub.3      130                      Ia-51                                                                              CF.sub.3    H --                                                                              --                                                                               ##STR179##   H CH.sub.3      152                      Ia-52                                                                              CF.sub.3    H --                                                                              --                                                                               ##STR180##   H CH.sub.3      162-5                    Ia-53                                                                              CF.sub.3    H --                                                                              --                                                                               ##STR181##   H CH.sub.3      124-5                    Ia-54                                                                              CF.sub.3    H --                                                                              --                                                                              H             H                                                                                ##STR182##   236                      Ia-55                                                                              CF.sub.3    H --                                                                              --                                                                              H             H                                                                                ##STR183##   114-116                  Ia-56                                                                              CF.sub.3    H --                                                                              --                                                                              H             H                                                                                ##STR184##   139-141                  Ia-57                                                                              CF.sub.3    H --                                                                              --                                                                              CH.sub.3      H                                                                                ##STR185##   148-150                  Ia-58                                                                              CF.sub.3    H --                                                                              --                                                                              CH.sub.3      H                                                                                ##STR186##   116-118                  Ia-59                                                                              CF.sub.3    H --                                                                              --                                                                              H             (CH.sub.2).sub.2 SCH.sub.2                                                                    188-190                  Ia-60                                                                              CF.sub.3    H --                                                                              --                                                                              H             (CH.sub.2).sub.3                                                                              184-186                  Ia-61                                                                              CF.sub.3    H --                                                                              --                                                                              H             H CH.sub.2 C(CH.sub.3).sub.3                                                                  178-180                  Ia-62                                                                              CF.sub.3    H --                                                                              --                                                                              CH.sub.3      H CH.sub.2 C(CH.sub.3).sub.3                                                                  173-175                  Ia-63                                                                              CF.sub.3    H --                                                                              --                                                                              H                                                                                            ##STR187##     232-234                  __________________________________________________________________________

EXAMPLE 5

Synthesis of the intermediates (III) ##STR188##

9.82 g (0.1 mol) of N-(α-cyanopropyl)-methylamine and 10.12 g oftriethylamine are dissolved in 120 ml of tetrahydrofuran and the mixtureis cooled to 0° C. 19.28 g (0.098 mol) of 2,4,6-trimethylphenylaceticacid chloride are then added dropwise in the course of one hour at 0° C.When the procedure has ended, the solution is introduced into a mixtureof 500 ml of glacial acetic acid and 50 ml of 1-normal HCl solution, andthe precipitate which is obtained in this process is filtered off anddried.

22.9 g (91% of theory) ofN-(α-cyanopropyl)-N-methyl-2,4,6-trimethylphenylacetamide are obtained.

EXAMPLE 6 ##STR189## Process aβ

1.2 g (0.12 mol) of sodium hydride are dissolved in 60 ml of absolutetoluene, and 22.5 g ofN-(α-cyanopropyl)-N-methyl-2,4,6-trimethylphenylacetamide, dissolved in100 ml of absolute toluene, are then added dropwise while cooling withan ice-bath. The mixture is then stirred until hydrogen is no longerevolved. The reaction solution is subsequently concentrated in vacuo,the residue is taken up in water, the mixture is acidified at 0°-20° C.using concentrated HCl solution, and the precipitate which is obtainedin this process is filtered off. This precipitate is dried in vacuo at70° C. using phosphorus pentoxide, if appropriate after previouslyhaving been extracted by boiling with a mixture of chloroform, methyltertiary butyl ether and n-hexane.

17.4 g (77.4% of theory) of4-amino-5-ethyl-1-methyl-3-(2,4,6-trimethylphenyl)-pyrrolin-2-one ofmelting point 192° C. are obtained.

EXAMPLE 7 ##STR190## Process bα

2.0 g (5.95 mMol) of4-amino-l-(3-fluorophenyl)-3-(3-trifluoromethylphenyl)-pyrrolin-2-one(Ia-1) and 40 ml of acetic acid chloride are refluxed for 4 hours. Theresulting suspension is introduced into 250 ml of ice-water whilecooling with an ice-bath and extracted three times using 100 ml portionsof methylene chloride, the collected organic phases are washed withsaturated ammonium chloride solution and dried with magnesium sulphate,and the methylene chloride is finally removed in vacuo.

The resulting pale grey solid is stirred with methyl tertiary butylether, the suspension is filtered, and the solid is dried.

1.3 g (57.8% of theory) of4-acetylamino-1-(3-fluorophenyl)-3-(3-trifluoromethylphenyl)-pyrrolin-2-oneof a melting point of 115° C. are obtained.

Analogous reactions are carried out following this general procedure.The yields differ between 35 and 90%. In individual cases the productwas chromatographed over silica gel (eluent toluene: acetone (3:1).

The end products of the formula (Ib) in which B represents acetyl andwhich are listed below in Table 4 are obtained analogously to Example 7and taking into consideration the information in the description ofprocess (bα) according to the invention.

                                      TABLE 4                                     __________________________________________________________________________     ##STR191##                                                 (Ib)              __________________________________________________________________________                                                              Melting             Ex. No.                                                                            X          Y Z n L            M  A           R       point/°C.    __________________________________________________________________________    Ib-2 CF.sub.3   H --                                                                              --                                                                              CH.sub.3     H                                                                                 ##STR192## CH.sub.3                                                                               80                 Ib-3 CF.sub.3   H --                                                                              --                                                                               ##STR193##  H  H           CH.sub.3                                                                              182-183             Ib-4                                                                                ##STR194##                                                                              H --                                                                              --                                                                              H            H                                                                                 ##STR195## CH.sub.3                                                                              162-163             Ib-5 CF.sub.3   H --                                                                              --                                                                              CH.sub.3     H  CH.sub.3    CH.sub.3                                                                              Resin               Ib-6 CF.sub.3   H --                                                                              --                                                                              H            H                                                                                 ##STR196## CH.sub.3                                                                              145                 Ib-7 CF.sub.3   H --                                                                              --                                                                              CH.sub.3     H  C.sub.2 H.sub.5                                                                           CH.sub.3                                                                               70                 Ib-8 CF.sub.3   H --                                                                              --                                                                              CH.sub.3     H                                                                                 ##STR197## CH.sub.3                                                                               96                 Ib-9 CF.sub.3   H --                                                                              --                                                                              H            H  i-C.sub.3 H.sub.7                                                                         CH.sub.3                                                                              143                 Ib-10                                                                              Cl         Cl                                                                              --                                                                              --                                                                              CH.sub.3     H  CH.sub.3    CH.sub.3                                                                              183                 Ib-11                                                                              H          H --                                                                              --                                                                              H            H                                                                                 ##STR198## CH.sub.3                                                                              219                 Ib-12                                                                              H          H --                                                                              --                                                                              H            H                                                                                 ##STR199## CH.sub.3                                                                               78                 Ib-13                                                                              CF.sub.3   H --                                                                              --                                                                              H            H                                                                                 ##STR200## CH.sub.3                                                                              236-237             __________________________________________________________________________                                                              Melting             Ex. No.                                                                            X          Y Z n M            L  A           R       point/°C.    __________________________________________________________________________    Ib-14                                                                              CF.sub.3   H --                                                                              --                                                                              H            H                                                                                 ##STR201## CH.sub.3                                                                              202                 Ib-15                                                                              Cl         H --                                                                              --                                                                              H            H                                                                                 ##STR202## CH.sub.3                                                                              234                 Ib-16                                                                              CF.sub.3   H --                                                                              --                                                                              H            (CH.sub.2).sub.4                                                                             CH.sub.3                                                                              165                 Ib-17                                                                              Cl         Cl                                                                              --                                                                              --                                                                              H            CH.sub.3                                                                         i-C.sub.4 H.sub.9                                                                         CH.sub.3                                                                              88-98               Ib-18                                                                              Cl         Cl                                                                              --                                                                              --                                                                              H            CH.sub.3                                                                         C.sub.2 H.sub.5                                                                           CH.sub.3                                                                              143-145             Ib-19                                                                              Cl         Cl                                                                              --                                                                              --                                                                              H            CH.sub.3                                                                          ##STR203## CH.sub.3                                                                              184-187             Ib-20                                                                              Cl         Cl                                                                              --                                                                              --                                                                              H            C.sub.2 H.sub.5                                                                  CH.sub.3    CH.sub.3                                                                              168-169             Ib-21                                                                              Cl         Cl                                                                              --                                                                              --                                                                              H            CH.sub.3                                                                          ##STR204## CH.sub.3                                                                              190-193             Ib-22                                                                              Cl         Cl                                                                              --                                                                              --                                                                              CH.sub.3     H  i-C.sub.3 H.sub.7                                                                         CH.sub.3                                                                              Resin               Ib-23                                                                              Cl         Cl                                                                              --                                                                              --                                                                              H            H                                                                                 ##STR205## CH.sub.3                                                                              265                 Ib-24                                                                              Cl         H --                                                                              --                                                                              H            H                                                                                 ##STR206## CH.sub.3                                                                              225-226             Ib-25                                                                              CF.sub.3   H --                                                                              --                                                                               ##STR207##  H  CH.sub.3    CH.sub.3                                                                               72                 Ib-26                                                                              Cl         Cl                                                                              --                                                                              --                                                                              H            H                                                                                 ##STR208## CH.sub.3                                                                              >250                __________________________________________________________________________                                                              Melting             Ex. No.                                                                            X          Y Z n L            M  A           R       point/°C.    __________________________________________________________________________    Ib-27                                                                              CF.sub.3   H --                                                                              --                                                                              H            H                                                                                 ##STR209## C.sub.2 H.sub.5                                                                       117                 Ib-28                                                                              CF.sub.3   H --                                                                              --                                                                              H            H                                                                                 ##STR210## C(CH.sub.3).sub.3                                                                     132                 Ib-29                                                                              CF.sub.3   H --                                                                              --                                                                              H            H                                                                                 ##STR211## CH.sub.2 C(CH.sub.3).sub                                                      .3      153                 Ib-30                                                                              CF.sub.3   H --                                                                              --                                                                               ##STR212##  H  CH.sub.3    CH.sub.3                                                                              54-57               Ib-31                                                                              CF.sub.3   H --                                                                              --                                                                               ##STR213##  H  CH.sub.3    CH.sub.3                                                                              115-117             Ib-32                                                                              CF.sub.3   H --                                                                              --                                                                               ##STR214##  H  CH.sub.3    CH.sub.3                                                                              145-147             Ib-33                                                                              CF.sub.3   H --                                                                              --                                                                               ##STR215##  H  CH.sub.3    CH.sub.3                                                                              75-77               __________________________________________________________________________                                                              Melting             Ex. No.                                                                            X          Y Z n M            L  A           R       point/°C.    __________________________________________________________________________    Ib-34                                                                              CF.sub.3   H --                                                                              --                                                                               ##STR216##  H  CH.sub.3    CH.sub.3                                                                              155-157             Ib-35                                                                              CF.sub.3   H --                                                                              --                                                                              H            H                                                                                 ##STR217## CH.sub.3                                                                              63-66               Ib-36                                                                              CF.sub.3   H --                                                                              --                                                                              H            H                                                                                 ##STR218## CH.sub.3                                                                              112-114             Ib-37                                                                              CF.sub.3   H --                                                                              --                                                                              CH.sub.3     H                                                                                 ##STR219## CH.sub.3                                                                              73-76               Ib-38                                                                              CF.sub.3   H --                                                                              --                                                                              CH.sub.3     H                                                                                 ##STR220## CH.sub.3                                                                              77-80               Ib-39                                                                              CF.sub.3   H --                                                                              --                                                                               ##STR221##  H  CH.sub.3    CH.sub.3                                                                              134-137             Ib-40                                                                              CF.sub.3   H --                                                                              --                                                                              H            CH.sub.2 CH.sub.2 SCH.sub.2                                                                  CH.sub.3                                                                              199-201             Ib-41                                                                              CF.sub.3   H --                                                                              --                                                                              H            CH.sub.2 CH.sub.2 CH.sub.2                                                                   CH.sub.3                                                                              128-130             Ib-42                                                                              CF.sub.3   H --                                                                              --                                                                              H            H  CH.sub.2 C(CH.sub.3).sub.3                                                                CH.sub.3                                                                              113-115             Ib-43                                                                              CF.sub.3   H --                                                                              --                                                                              CH.sub.3     H  CH.sub.2 C(CH.sub.3).sub.3                                                                CH.sub.3                                                                              159-160             Ib-44                                                                              CF.sub.3   H --                                                                              --                                                                               ##STR222##  H  CH.sub.3    CH.sub.3                                                                              93-95               __________________________________________________________________________

USE EXAMPLES

In the use examples which follow, the compound listed below was employedas comparison substance: ##STR223##1-Methyl-3-phenyl-5-(2,α,α-trifluoro-m-tolyl)-4-pyridone [fluridone],known from R. Wegler, Chemie der Pflanzenschutz undSchadlingsbekaimpfungsmittel [Chemistry of Crop Protection andPesticides] 5, Herbizide, Axel-Springer-Verlang, Berlin, Heidelberg, NewYork 1977, page 309.

EXAMPLE A

Post-emergence Test

    ______________________________________                                        Solvent:    5 parts by weight of acetone                                      Emulsifier: 1 part by weight of alkylaryl polyglycol                                      ether                                                             ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of the active compound in such a way as to apply theparticular amounts of active compound desired per unit area. After threeweeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction

A clearly superior activity and crop plant selectivity compared with theprior art is shown, in this test, for example by the compounds of thefollowing Preparation Examples Ia-2, Ia-3, Ia-11, Ib-6 and Ib-9.

EXAMPLE B

Pro-emergence Test

    ______________________________________                                        Solvent:       5 parts by weight of acetone                                   Emulsifier:    1 part by weight of alkylaryl                                                 polyglycol ether                                               ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It is expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation is of no importance, only theamount of active compound applied per unit area being decisive. Afterthree weeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction

A clearly superior activity and crop plant selectivity compared with theprior art is shown, in this test, for example by the compounds of thefollowing Preparation Example: Ib-9.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

What is claimed is:
 1. A 4-(substituted)amino-3-arylpyrrolinonederivative of the general formula (I) wherein ##STR224## X representshydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy,n- or i-propoxy, trifluoromethyl, trifluoromethoxy, orY representshydrogen, fluorine, chlorine, bromine, methyl, methoxy, trifluoromethoxyor trifluoromethyl, n represents 0 and A represents methyl, ethyl,n-propyl, iso-propyl, n-, iso-, sec.- or tert.-butyl, or represents anin each case straight-chain or branched radical from the seriescomprising pentyl, hexyl, heptyl, octyl, halogeno-C₁ -C₃ -alkyl, allyl,propargyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl,cyclopropyl, cyclopentyl, cyclohexyl, or represents phenyl or benxyl,each of which is unsubsttituted or monosubstituted to trisubstituted byidentical or different substituents from the series comprising fluorine,chlorine, trifluoromethyl, B represents hydrogen, the group --CO--R orthe group ##STR225## L represents hydrogen or an optionallyhalogen-substituted straight-chain or branched radical from the seriescomprising C₁ -C₈ -alkyl, cycloalkyl which has 3 to 6 ring atoms or arylwhich is optionally substituted by fluorine, chlorine, bromine, methyl,ethyl, propyl, iso-propyl, methoxy, ethoxy, trifluoromethyl or nitro, Mrepresents hydrogen or a straight-chain or branched radical from theseries comprising C₁ -C₆ -alkyl,or in which A and L or L and M togetherwith the atoms to which they are bonded form a 3 to 6-membered ring,optionally substituted by C₁ -C₄ -alkyl, and/or interrupted byoxygen/sulphur, R represents an optionally halogen-substitutedstraight-chain or branched radical from the series comprising C₁ -C₈-alkyl, C₁ -C₄ -alkenyl, C₁ -C₆ -alkoxy-C₂ -C₄ -alkyl, cycloalkyl whichhas 3 to 6 ring atoms and the enantiomeric compounds of the formula (I)with the exception of the compounds:4-amino-1-cyclopropyl-3-(3-trifluoromethylphenyl)-3-pyrrolin-2-one and4-amino-1-isopropyl-3-(3-trifluoromethylphenyl)-3-pyrrolin-2-one.
 2. Acompound according to claim 1, wherein such compound is4-amino-1-cyclopropyl-5-methyl-3-phenyl-pyrrolin-2-one of the formula##STR226##
 3. A compound according to claim 1 wherein such compound is4-amino-1-isopropyl-3-phenyl-pyrrolin-2-one of the formula ##STR227## 4.A compound according to claim 1, wherein such compoundis4-acetylamino-1-cyclopropyl-3-(3-trifluoromethyl-phenyl)-pyrrolin-2-oneof the formula ##STR228##
 5. A compound according to claim 1, whereinsuch compoundis4-acetylamino-1-isopropyl-3-(3-trifluoromethylphenyl)-pyrrolin-2-oneof the formula ##STR229##
 6. A herbicidal composition comprising aherbicidally effective amount of a compound according to claim 1 and adiluent.
 7. A method of combating unwanted vegetation which comprisesapplying to such vegetation or to a locus from which it is desired toexclude such vegetation a herbicidally effective amount of a compoundaccording to claim
 1. 8. A method according to claim 7, wherein suchcompound is4-amino-1-cyclopropyl-5-methyl-3-phenyl-pyrrolin-2-one4-amino-1-isopropyl-3-phenyl-pyrrolin-2-one4-acetylamino-1-cyclopropyl-3-(3-trifluoromethylphenyl)-pyrrolin-2-one4-acetylamino-1-isopropyl-3-(3-trifluoromethylphenyl)-pyrrolin-2-one.